EP2680351B1 - Procédé de fabrication d'un catalyseur d'électrode pour pile à combustible - Google Patents

Procédé de fabrication d'un catalyseur d'électrode pour pile à combustible Download PDF

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Publication number
EP2680351B1
EP2680351B1 EP12748862.5A EP12748862A EP2680351B1 EP 2680351 B1 EP2680351 B1 EP 2680351B1 EP 12748862 A EP12748862 A EP 12748862A EP 2680351 B1 EP2680351 B1 EP 2680351B1
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Prior art keywords
fuel cell
catalyst
transition metal
producing
cell electrode
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German (de)
English (en)
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EP2680351A1 (fr
EP2680351A4 (fr
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Masaki Horikita
Kunchan Lee
Yasuaki Wakizaka
Takashi Sato
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Resonac Holdings Corp
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Showa Denko KK
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9008—Organic or organo-metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for producing a fuel cell electrode catalyst and a method for producing a fuel cell electrode or the like and more particularly relates to a method for producing a fuel cell catalyst useful as a catalyst substituted for noble metals such as platinum and a fuel cell electrode or the like.
  • a polymer electrolyte fuel cell is a fuel cell in the form in which a polymer solid electrolyte is sandwiched between an anode and a cathode, a fuel is supplied to the anode, and oxygen or air is supplied to the cathode, whereby oxygen is reduced at the cathode to produce electricity.
  • a fuel is supplied to the anode
  • oxygen or air is supplied to the cathode, whereby oxygen is reduced at the cathode to produce electricity.
  • hydrogen, methanol, or the like is mainly used.
  • a layer containing a catalyst (hereinafter also referred to as a "fuel cell catalyst layer”) has been conventionally disposed on the surface of a cathode (air electrode) or the surface of an anode (fuel electrode) of the fuel cell.
  • noble metals have been generally used, and, among the noble metals, a noble metal stable at a high potential and having a high activity, such as platinum or palladium, has been mainly used.
  • a noble metal stable at a high potential and having a high activity such as platinum or palladium.
  • these noble metals are expensive and limited in resource amount, development of substitutable catalysts has been desired.
  • noble metals As a catalyst substituted for noble metals, those entirely free of noble metals, such as base metal carbides, base metal oxides, base metal carbonitroxides, chalcogen compounds, and carbon catalysts, have been reported (for example, see Patent Literature 1 to Patent Literature 4). These materials are inexpensive and abundant in resource amounts as compared with noble metal materials such as platinum.
  • Patent Literature 3 and Patent Literature 4 although exhibiting high oxygen reduction catalytic activity, have a problem that stability under fuel cell operating conditions is not sufficient.
  • Patent Literature 5 and Patent Literature 6 As a catalyst substituted for noble metals, Nb and Ti carbonitroxides in Patent Literature 5 and Patent Literature 6 can effectively express the above-described performance and thus have received particular attention.
  • Patent Literature 5 and Patent Literature 6 have extremely high performance as compared with conventional catalysts substituted for noble metals, a portion of the production step thereof needs to include heat treatment under a high temperature of 1600°C to 1800°C (for example, Example 1 of Patent Literature 5 or Example 1 of Patent Literature 6) .
  • Patent Literature 7 reports a technology relating to the production of a carbon-containing titanium oxynitride that contains carbon, nitrogen, and oxygen.
  • the production of the carbon-containing titanium oxynitride requires two-stage synthesis: the production of a titanium oxynitride by reacting a nitrogen-containing organic compound with a titanium precursor; and the production of a carbon-containing titanium oxynitride by reacting a phenol resin with the titanium oxynitride precursor, and thus involves complicated steps.
  • the production of the titanium oxynitride precursor requires complicated steps including stirring, heating, and refluxing at 80°C as well as cooling and concentrating under reduced pressure, thus resulting in high production cost.
  • the phenol resin is a thermosetting resin having a three-dimensional network structure, it is difficult to homogenously mix and react the phenol resin with a metal oxide.
  • the thermal decomposition temperature of the phenol resin is 400°C to 900°C, a carbonization reaction due to the complete decomposition of the phenol resin is unlikely to take place at a temperature of 1000°C or less.
  • Patent Literature 7 and Non-Patent Literature 1 only describe applications to a thin film for a solar collector and a photocatalyst as uses thereof, failing to disclose or examine a method for producing a metal carbonitroxide having particulate or fibrous shape or the like that is highly useful as an electrode catalyst and uses thereof.
  • Patent Literature 8 discloses a method for producing an electrode catalyst characterized by burning a mixed material of an oxide and a carbon material precursor but an electrode catalyst having sufficient catalytic performance has not been obtained.
  • Patent Literature 9 discloses a fuel cell electrode catalyst prepared by using a polynuclear complex of cobalt and the like but this catalyst has had problems that a cost is high and its catalytic activity is insufficient.
  • Non-Patent Literature 2 discloses a method for producing an electrode catalyst characterized by burning a mixed material of a titanium alkoxide and a carbon material precursor but the production step does not use an organic substance containing nitrogen and thus an electrode catalyst having sufficient catalytic performance has not been obtained.
  • Patent Literature 10 discloses a method for producing an electrode catalyst, comprising burning a metal compound, such as zirconium hydroxide, and a carbon material precursor, under a condition where the carbon material precursor can transit to a carbon material (e.g., 400 to 1100°C) but an electrode catalyst having sufficient catalyst performance has not been obtained.
  • a metal compound such as zirconium hydroxide
  • a carbon material precursor e.g. 400 to 1100°C
  • Patent Literature 11 discloses a method for producing a fuel cell electrode catalyst, comprising: a step 1 of mixing at least a compound containing a transition metal (element of group 4 or group 5 of the periodic table), a nitrogen-containing organic compound, and a solvent to obtain a catalyst precursor solution; a step 2 of removing the solvent from the catalyst precursor solution; and a step 3 of heat-treating a solid residue, obtained in the step 2, at comparatively low temperature, to obtain an electrode catalyst, but does not disclose a method for producing a fuel cell electrode catalyst, comprising a step of bringing an aqueous solution of a transition metal compound (1) into contact with ammonia and/or ammonia water to generate a precipitate containing an atom of the transition metal, as described below.
  • a method for producing a fuel cell electrode catalyst comprising a step of bringing an aqueous solution of a transition metal compound (1) into contact with ammonia and/or ammonia water to generate a precipitate containing an atom of the transition metal, as described
  • WO 2010/110469 A1 and WO 2008/146823 A2 disclose a method for producing a fuel cell electrode catalyst comprising a step of bringing an aqueous solution of a transition metal compound into contact with ammonia water to generate a precipitate. The precipitate is then mixed with carboxylic acids and heated to obtain an electrode catalyst.
  • An object of the present invention is to provide a method for producing a fuel cell electrode catalyst having high catalytic activity using a transition metal (such as titanium) through heat treatment at comparatively low temperature according to claim 1.
  • a transition metal such as titanium
  • the present invention relates to the following [1] to [10].
  • a fuel cell electrode catalyst having high catalytic activity using a transition metal (such as titanium) through heat treatment at comparatively low temperature.
  • the method for producing a fuel cell electrode catalyst of the present invention comprises:
  • an atom and an ion are not strictly distinguished from each other unless special circumstance requires otherwise, and are referred to as an "atom" .
  • an aqueous solution of a transition metal compound (1) is brought into contact with ammonia and/or ammonia water to generate a precipitate (A) containing an atom of the transition metal.
  • the precipitate (A) contains a hydroxide of the transition metal.
  • the contact operation is preferably carried out by adding the aqueous solution of the transition metal compound (1) to the ammonia water.
  • This allows a catalyst that has higher dispersibility and is excellent in coating property to be obtained.
  • This may be carried out by blowing ammonia into or adding ammonia water to the aqueous solution of the transition metal compound (1) .
  • the aqueous solution of the transition metal compound (1) is dropwise added little by little to the ammonia water (i.e., the whole amount is not added at a time).
  • the precipitate (A) is collected and is provided to the step (II) described below.
  • the collection of the precipitate (A) may be carried out by centrifuging or filtrating an aqueous solution containing the precipitate (A) and is preferably carried out by centrifugation.
  • the collection of the precipitate (A) by the centrifugation is carried out by a series of operations of the centrifugation of the aqueous solution containing the precipitate (A) and the removal of supernatant liquid.
  • the entirety of the supernatant liquid may be removed or only a portion thereof may be removed. In the case of the latter, the precipitate (A) with the supernatant liquid is provided to the subsequent step (II).
  • the collection by the centrifugation is preferred in terms of allowing even smaller particles of the precipitate (A) to be provided to the subsequent step, so that a catalyst having a higher specific surface area is obtained and activity per unit mass of the catalyst becomes high.
  • the centrifugation is preferably carried out plural times (e.g., 2 to 7 times). That is, it is preferable to repeat the operations of the addition of water to the collected precipitate (A), (optionally stirring), the centrifugation, and the removal of the supernatant liquid.
  • the precipitate (A) is purified by repeating the centrifugation.
  • the centrifugation is carried out under conditions such that, e.g., rotation number is 500 to 20000 rpm and time is 5 to 120 minutes.
  • the collection of the precipitate (A) by the filtration may be carried out by using filter paper or a filtration membrane or by repeating the operations of the addition of water to the collected precipitate (A), (optionally stirring), the filtration, and the removal of the filtrate with the use of an ultrafiltration membrane while purifying the precipitate (A).
  • This precipitate may be a gelatinous substance.
  • a portion or the entirety of the transition metal compound (1) is a compound containing, as a transition metal element, at least one transition metal element M1 selected from the elements of group 4 and group 5 of the periodic table.
  • the transition metal element M1 include titanium, zirconium, hafnium, niobium, vanadium, and tantalum. These may be used singly or in combination of two or more kinds.
  • transition metal elements M1 from the viewpoint of a cost and the performance of the resultant catalyst, titanium, zirconium, niobium, and tantalum are preferred, and titanium and zirconium are further preferred.
  • the reserves of these metals in the earth crust are particularly large and thus enable products to be steadily supplied, therefore leading to higher industrial advantage.
  • transition metal compound (1) examples include metal sulfates, metal halides, metal alkoxides, metal acetates, metal phosphates, metal nitrates, metal organic acid salts, metal acid halides (intermediate hydrolysates of metal halides), metal perhalates, metal hypohalites, and metal complexes, and metal sulfates and metal halides are preferred.
  • metal halides examples include chlorides, bromides, and iodides of the transition metals, and chlorides of the transition metals are preferred because of having high safety during use thereof.
  • metal alkoxides methoxide, propoxide, isopropoxide, ethoxide, butoxide, and isobutoxide of the transition metals are preferred; and isopropoxide, ethoxide, and butoxide of the transition metals are further preferred.
  • the metal alkoxide may have one kind of alkoxy group or may have two or more kinds of alkoxy groups.
  • Examples of the metal halides include chlorides, bromides, and iodides of the transition metals
  • examples of the metal acid halides include acid chlorides, acid bromides, and acid iodides of the transition metals.
  • Examples of the metal acid halides include metal acid chlorides, examples of the metal perhalates include metal perchlorates, and examples of the metal hypohalites include metal hypochlorites.
  • transition metal compound (1) examples include:
  • titanium sulfate, titanium tetrachloride, niobium sulfate, niobium pentachloride, zirconium sulfate, zirconium tetrachloride, zirconium oxychloride, tantalum sulfate, and tantalum pentachloride are preferred; and titanium sulfate and titanium tetrachloride are further preferred.
  • the aqueous solution of the transition metal compound (1) may be brought into contact with ammonia and/or ammonia water in the presence of a transition metal compound (2).
  • a transition metal compound (2) there is used a transition metal compound that is different from the transition metal compound (1) and contains, as a transition metal element, at least one transition metal element M2 selected from iron, nickel, chromium, cobalt, and manganese (hereinafter also referred to as "transition metal element M2" or "M2").
  • transition metal element M2 transition metal element selected from iron, nickel, chromium, cobalt, and manganese
  • transition metal element M2 iron and chromium are preferred, and iron is further preferred, because of having high catalyst performance per unit cost.
  • transition metal compound (2) examples include:
  • iron(II) chloride, iron(III) chloride, potassium ferrocyanide, potassium ferricyanide, ammonium ferrocyanide, ammonium ferricyanide, iron(II) acetate, iron(II) lactate, nickel(II) chloride, nickel(II) acetate, nickel(II) lactate, chromium(II) chloride, chromium(III) chloride, chromium(II) acetate, chromium(III) acetate, chromium(III) lactate, cobalt(II) chloride, cobalt(III) chloride, cobalt(II) acetate, cobalt(II) lactate, manganese(II) chloride, manganese(II) acetate, and manganese(II) lactate are preferred since the activity of a catalyst obtained with the compound as a raw material becomes high; iron(II) chloride, iron(III) chloride, potassium ferrocyan
  • step (II) at least the precipitate (A), an organic compound (B) (described in detail below), and a liquid medium (C) are mixed to prepare a catalyst precursor liquid.
  • the mixing operation may be carried out by: mixing the organic compound (B) and the liquid medium (C) to prepare a solution (or dispersion) of the organic compound (B); and then mixing the solution (or the dispersion) and the precipitate (A) . By mixing the precipitate (A) and the organic compound (B) in the presence of the liquid medium (C), these can be mixed evenly.
  • the precipitate (A) may be added little by little to the solution or dispersion of the organic compound (B) (i.e., the whole amount is not added at a time).
  • the precipitate (A), the organic compound (B), and the liquid medium (C) may be put in a pressure-applicable container such as an autoclave and mixed with being pressurized at a pressure of ordinary pressure or more.
  • organic compound (B) examples include:
  • nitrogen-containing polymer compound a polymer compound containing a nitrogen atom in the molecule
  • amino acid a polymer compound containing a nitrogen atom in the molecule
  • polyvinylpyrrolidone, glucosamine, and glycine are further preferred.
  • any of an organic compound containing nitrogen in the molecule may be used.
  • the ratio (B/A) of the total number B of the carbon atoms of the organic compound (B) used in the step (II) to the total number A of the atoms of the transition metal elements of the transition metal compounds used in the production method of the present invention is preferably 1 or more and 200 or less, more preferably 1.5 or more and 150 or less, 2 or more and 130 or less, further preferably 3 or more and 80 or less, further more preferably 4 or more and 60 or less, particularly preferably 5 or more and 30 or less, in terms of allowing the heat treatment in the step (IV) to be performed while decreasing components eliminating as carbon compounds such as carbon dioxide and carbon monoxide, i.e., decreasing an emission gas during catalyst production and in terms of allowing a resultant catalyst to have high activity.
  • the ratio (C/A) of the total number C of the nitrogen atoms of the nitrogen-containing organic compound used in the step (II) to the total number A of the atoms of the transition metal elements of the transition metal compounds used in the production method of the present invention is 1 or more and 28 or less, more preferably 1.5 or more and 17 or less, further preferably 2 or more 12 or less, more further preferably 2.5 or more and 10 or less, particularly preferably 3.5 or more and 8.5 or less, from the viewpoint of obtaining a catalyst with good oxygen reduction activity.
  • liquid medium (C) examples include water, alcohols, and aqueous solution or alcohol solution of acids.
  • alcohols preferred are ethanol, methanol, butanol, propanol, and ethoxyethanol; and further preferred are ethanol and methanol.
  • acids acetic acid, nitric acid, hydrochloric acid, phosphoric acid, and citric acid are preferred; and when these acids are liquid, these may be used without being processed or may be used in the form of an aqueous solutions or an alcohol solution.
  • acids acetic acid and nitric acid are further preferred since the oxygen reduction activity of a resultant catalyst is enhanced.
  • Water, alcohols, and acids may be used singly or in combination of two or more kinds.
  • the transition metal compound (2) as well as the precipitate (A), the organic compound (B), and the liquid medium (C) may be further mixed.
  • the performance of the resultant catalyst is improved by using the transition metal compound (M2) .
  • the mixing operation in the case of mixing the transition metal compound (2) may be carried out by: mixing the organic compound (B), the transition metal compound (2), and the liquid medium (C) to prepare a solution (or dispersion); and then mixing the solution (or the dispersion) and the precipitate (A).
  • the liquid medium (C) in the case of providing the precipitate (A) with supernatant liquid to the step (II), also the supernatant liquid is removed from the catalyst precursor liquid obtained in the step (II).
  • the removal of the liquid medium (C) may be performed in air, or may be performed under an atmosphere of an inert gas (for example, nitrogen, argon, helium). It is preferable to use the inert gas since the activity of the resultant catalyst becomes high; among the inert gases, from the viewpoint of a cost, nitrogen and argon are preferred; and nitrogen is more preferred.
  • an inert gas for example, nitrogen, argon, helium
  • the temperature in the removal of the liquid medium (C) may be ordinary temperature when the vapor pressure of the liquid medium (C) is large, but from the viewpoint of mass production of the catalyst, temperature is preferably 30°C or more, more preferably 40°C or more, further preferably 50°C or more; and from the viewpoint of preventing the decomposition of the catalyst precursor contained in the liquid obtained in the step (II), the temperature is preferably 250°C or less, more preferably 150°C or less, further preferably 110°C or less.
  • the removal of the liquid medium (C) may be performed under atmospheric pressure when the vapor pressure of the liquid medium (C) is high, but is preferably performed under reduced pressure (e.g., 0.1 Pa to 0.1 MPa) in order to remove the liquid medium (C) within a shorter period of time.
  • reduced pressure e.g., 0.1 Pa to 0.1 MPa
  • an evaporator may be used for the removal of the liquid medium (C) under reduced pressure.
  • the removal of the liquid medium (C) may be performed with the mixture obtained in the step (II) being allowed to stand still. In order to obtain a more homogenous solid residue, preferred is the removal of the liquid medium (C) with the mixture being rotated.
  • the solution is rotated using a stirring rod, a stirring blade, a stirring bar, or the like.
  • the removal of the liquid medium (C) is performed while regulating the vacuum degree of a container holding the mixture, in which case the drying is performed in a sealable container, it is preferable that the removal of the liquid medium (C) is performed while the whole container is rotated: for example, it is preferable that the removal of the liquid medium (C) is performed using e.g., a rotary evaporator.
  • the solid residue obtained in the step (III) may have a non-uniform composition or be at a non-uniform agglomeration state.
  • the solid residue may be subjected to mixing and crushing to obtain more uniform and finer powders to be used in the step (IV), whereby a catalyst can be obtained which has more uniform particle diameter.
  • a roll-rotating mill for example, a ball mill, a small-diameter ball mill (bead mill), a medium-stirring mill, an air flow crusher, a mortar, an automatic kneading mortar, a crushing tank, or a jet mill is employable; when the solid residue has been provided in a small amount, a mortar, an automatic kneading mortar, or a batch-type ball mill is preferably used.
  • a jet mill is preferably used.
  • step (IV) a solid in the catalyst precursor liquid is subjected to heat treatment.
  • the catalyst precursor liquid containing the solid obtained in the step (II) may be heat-treated without being processed or the solid residue obtained in the step (III) may be heat-treated.
  • the temperature in this heat treatment is 600 to 1200°C, preferably 600 to 1100°C, more preferably 700 to 1050°C.
  • Examples of methods of the heat treatment method include a standing method, a stirring method, a dropping method, and a powder capturing method.
  • the standing method is a method in which the solid residue obtained in the step (III) is placed in a stationary electric furnace or the like and is heated. During the heating, the solid residue that has been weighed may be put in a ceramic container such as an alumina board or a quartz board.
  • the standing method is preferable in view of being able to heat a large amount of the solid residue.
  • the stirring method is a method in which the solid residue is put in an electric furnace such as a rotary kiln and is heated while being stirred.
  • the stirring method is preferable in view of being able to heat a large amount of the solid residue and in view of being able to prevent the aggregation and growth of the particles of the resultant electrode catalyst. Furthermore, the stirring method is preferable in view of being able to continuously produce the electrode catalyst by sloping a furnace.
  • the dropping method is a method in which an induction furnace is heated to a predetermined heating temperature while flowing, e.g., an inert gas containing a very small amount of an oxygen gas as an atmosphere gas through the furnace, a thermal equilibrium is maintained at the temperature, and thereafter the solid residue is dropped and heated in a crucible which is a heating zone in the furnace.
  • the dropping method is preferable in view of being able to minimizing the aggregation and growth of the particles of the resultant electrode catalyst.
  • the powder capturing method is a method in which the solid residue is caused to suspend as particles in an inert gas atmosphere containing a trace amount of an oxygen gas and the solid residue is captured and heated in a vertical tubular furnace kept at a predetermined heating temperature.
  • a temperature-raising rate which is not particularly limited, is preferably around 1°C/min to 100°C/min, more preferably 5°C/min to 50°C/min.
  • the heating time is preferably 0.1 to 10 hours, more preferably 0.5 to 5 hours, further preferably 0.5 to 3 hours.
  • the time of heating electrode catalyst particles is 0.1 to 10 hours, preferably 0.5 hour to 5 hours. The heating time in this range is preferred in view of leading to the formation of uniform electrode catalyst particles and allowing a catalyst having high activity to be obtained.
  • the heating time of the solid residue is usually 10 minutes to 5 hours, preferably 30 minutes to 2 hours.
  • the heating time is defined as a mean residence time calculated from the sample flowing amount in a steady furnace.
  • the heating time of the solid residue is usually 0.5 to 10 minutes, preferably 0.5 to 3 minutes.
  • the heating time within this range leads to the tendency of the formation of uniform electrode catalyst particles.
  • the heating time of the solid residue is 0.2 second to 1 minute, preferably 0.2 to 10 seconds.
  • the heating time within this range leads to the tendency of the formation of uniform electrode catalyst particles.
  • a heating furnace employing LNG (liquefied natural gas), LPG (liquefied petroleum gas), light oil, heavy oil, electricity, or the like as a heat source may be used as a heat treatment apparatus.
  • LNG liquefied natural gas
  • LPG liquefied petroleum gas
  • light oil a heating apparatus that provides heating from the outside of the furnace.
  • a heating furnace which provides the solid residue in an amount of 50 kg or more per one batch, from the viewpoint of a cost, a heating furnace employing LNG or LPG as a heat source is preferable.
  • an electric furnace employing electricity as a heat source, which allows for the strict controlling of temperature.
  • Exemplary shapes of the furnace include a tubular furnace, a top-loading furnace, a tunnel furnace, a box furnace, a sample table elevating-type furnace (elevator furnace), a car-bottom furnace, and the like; of these, preferred are a tubular furnace, a top-loading furnace, a box furnace, and a sample table elevating-type furnace, which allow for the particular strict controlling of atmosphere; and preferred are a tubular furnace and a box furnace.
  • the above heat source is also employable; however, especially when the solid residue is continuously heat-treated by the stirring method using a inclined rotary kiln, it is likely that the equipment size becomes larger and a large amount of energy is needed; and thus it is preferable to use a heat source derived from fuels such as LPG.
  • the atmosphere in performing the heat treatment is preferably nitrogen, argon, and helium, further preferably nitrogen and argon, from the viewpoint of allowing the resultant electrode catalyst to have increased activity. These may be used singly or in combination of two or more kinds.
  • the organic compound (B) is an organic compound that does not contain nitrogen in the molecule, it is preferable to perform the heat treatment at a temperature of 800°C or more under the atmosphere of a nitrogen gas from the viewpoint of allowing the resultant electrode catalyst to have increased activity.
  • the presence of a reactive gas in the atmosphere in performing the heat treatment may allow the resultant electrode catalyst to have higher catalytic performance.
  • the reactive gas include carbon-containing gases such as oxygen gas, hydrogen gas, and methane; and nitrogen-containing gases such as ammonia.
  • the concentration of the hydrogen gas is, for example, 100% by volume or less, preferably 0.01 to 10% by volume, more preferably 1 to 5% by volume.
  • the concentration of the oxygen gas is, for example, 0.01 to 10% by volume, preferably 0.01 to 5% by volume.
  • a heat-treated product may be crushed.
  • Performing the crushing may improve the processability in using the resultant electrode catalyst to produce an electrode, and the properties of the resultant electrode.
  • a roll-rotating mill for example, a ball mill, a small-diameter ball mill (bead mill), a medium-stirring mill, an air flow crusher, a mortar, an automatic kneading mortar, a crushing tank, or a jet mill may be used.
  • a mortar When the electrode catalyst has been provided in a small amount, a mortar, an automatic kneading mortar, or a batch-type ball mill is preferred; and when the heat-treated product is to be continuously treated in a large amount, a jet mill or a continuous-type ball mill is preferred, and among the continuous-type ball mills, a bead mill is further preferred.
  • the fuel cell electrode catalyst of the present invention is produced by the above-described method for producing a fuel cell electrode catalyst of the present invention (hereinafter, the fuel cell electrode catalyst produced by the above-described method for producing a fuel cell electrode catalyst of the present invention is also referred to simply as "catalyst").
  • the range of x is more preferably 0.15 ⁇ x ⁇ 5.0, further preferably 0.2 ⁇ x ⁇ 4.0, particularly preferably 1.0 ⁇ x ⁇ 3.0;
  • the range of y is more preferably 0.01 ⁇ y ⁇ 1.5, further preferably 0.02 ⁇ y ⁇ 0.5, particularly preferably 0.03 ⁇ y ⁇ 0.4; and the range of z is more preferably 0.6 ⁇ z ⁇ 2.6, further preferably 0.9 ⁇ z ⁇ 2.0, particularly preferably 0.95 ⁇ z ⁇ 1.5.
  • the catalyst contains, as the transition metal element, one transition metal element M1 selected from the group consisting of the group 4 and the group 5 elements of the periodic table and at least one transition metal element M2 selected from iron, nickel, chromium, cobalt, and manganese
  • the catalyst, by containing M2 in this proportion, has higher performance.
  • x, y, and z are as described above; and the range of a is more preferably 0.01 ⁇ a ⁇ 0.5, further preferably 0.015 ⁇ a ⁇ 0.4, particularly preferably 0.02 ⁇ a ⁇ 0.2.
  • a, x, y, and z are those as measured by the method adopted in Examples described later.
  • transition metal element M2 metal element that is at least one element selected from iron, nickel, chromium, cobalt, and manganese
  • the catalyst of the present invention preferably has a transition metal element atom, a carbon atom, a nitrogen atom and an oxygen atom, and has a crystalline structure of an oxide, a carbide or a nitride of the transition metal element, or a plurality of crystalline structures thereof.
  • the catalyst has an oxide structure of the transition metal element with the site of the oxygen atom of the oxide structure being substituted with a carbon atom or nitrogen atom; or has a carbide, nitride or carbonitride structure of the transition metal element with the site of the carbon atom or the nitrogen atom being substituted with an oxygen atom; or has a mixed structure containing such structures.
  • a fuel cell electrode catalyst having a large specific surface area is produced, and the specific surface area as calculated by BET method of the catalyst of the present invention is preferably 30 to 350 m 2 /g, more preferably 50 to 300 m 2 /g, further preferably 100 to 300 m 2 /g.
  • the specific surface area within the above range preferably allows the catalyst to have high activity since the structure of the catalyst is more preferably maintained and, furthermore, a surface area per unit weight is large.
  • the oxygen reduction current density of the fuel cell electrode catalyst produced by the production method of the present invention can be determined in such as manner as described below. That is, from the result of a measurement method (A) described below, a difference between the reduction current under oxygen atmosphere and the reduction current under nitrogen atmosphere at a specific potential (e.g., 0.7 V) is calculated, and the calculated value is further divided by an area of the electrode to provide a value and this value is defined as an oxygen reduction current density (mA/cm 2 ).
  • a catalyst and carbon are added to a solvent so that the catalyst dispersed in the carbon being electron conductive particles accounts for 1% by mass.
  • the mixture is ultrasonically stirred to give a suspension.
  • the carbon source herein is carbon black (specific surface area: 100-300 m 2 /g) (e.g., XC-72 manufactured by Cabot Corporation), and the catalyst is dispersed therein with a catalyst:carbon mass ratio of 95:5.
  • a 10 ⁇ L portion thereof is collected and is quickly dropped on a glassy carbon electrode (diameter: 5.2 mm) and dried at 120°C for 5 minutes to form a fuel cell catalyst layer containing the catalyst on the glassy carbon electrode. This dropping and drying operation is performed until 1.0 mg or more of the fuel cell catalyst layer is formed on the carbon electrode surface.
  • polarization is carried out in a 0.5 mol/L sulfuric acid aqueous solution at 30°C under an oxygen atmosphere and a nitrogen atmosphere at a potential scanning rate of 5 mV/sec, thereby recording a current-potential curve.
  • the oxygen reduction current density of the fuel cell electrode catalyst produced by the production method of the present invention at 0.7 V is preferably 0.08 mA/cm 2 or more and 10 mA/cm 2 or less, more preferably 0.1 mA/cm 2 or more and 9 mA/cm 2 or less, further preferably 0.2 mA/cm 2 or more and 8 mA/cm 2 or less, particularly preferably 0.3 mA/cm 2 or more and 7 mA/cm 2 or less, for use as a polymer electrolyte fuel cell air electrode catalyst.
  • the fuel cell electrode catalyst produced by the production method of the present invention can be used as a catalyst alternative to a platinum catalyst.
  • the fuel cell catalyst layer produced by the method for producing a fuel cell electrode catalyst layer of the present invention comprises the catalyst.
  • Fuel cell catalyst electrode layers include anode catalyst layers and cathode catalyst layers, and the catalyst may be used in any one of these layers. Because the catalyst has excellent durability and high oxygen reducing ability, it is preferably used in cathode catalyst layers.
  • the fuel cell electrode catalyst layer of the present invention preferably further comprises an electron conductive powder.
  • the reduction current can be more increased. It is considered that the electron conductive powder increases the reduction current because of allowing the catalyst to have an electrical bond for inducing electrochemical reaction.
  • the electron conductive particles are usually used as a carrier of the catalyst.
  • the catalyst in order for the catalyst to be given more electrons or in order for a reactant to receive many electrons from the catalyst, the catalyst, in order to be provided with conductivity, may be mixed with carrier particles.
  • the carrier particles may be mixed into the catalyst produced after subjected to the step (I) to the step (IV), or may be mixed in any stage of from the step (II) to the step (IV).
  • the electron conductive particles examples include carbon, conductive polymers, conductive ceramics, metals, and conductive inorganic oxides such as tungsten oxide and iridium oxide, and these materials can be used singly or in combination with one another.
  • carbon or a mixture of carbon and other electron conductive particles is preferred, since the electron conductive particles composed of carbon have a large specific surface area, those having a small particle diameter are easily available inexpensively, and they are excellent in chemical resistance and high-potential resistance.
  • the fuel cell catalyst layer preferably comprises the catalyst and carbon particles.
  • the carbon examples include carbon black, graphite, activated carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, fullerene, porous carbon, graphene, and the like. If the particle diameter of the electron conductive particles composed of carbon is excessively small, an electron conductive path is not readily formed, while if the particle diameter is within the following ranges, the fuel cell catalyst layer has more improved gas diffusion properties or the catalyst usage rate is more improved, and, therefore, the particle diameter of the electron conductive particles composed of carbon is preferably 10 to 1000 nm, more preferably 10 to 100 nm.
  • the weight ratio of the catalyst to the electron conductive particles is preferably 4:1 to 1000:1.
  • the conductive polymers are not particularly limited but examples thereof include polyacetylene, poly-p-phenylene, polyaniline, polyalkylaniline, polypyrrole, polythiophene, polyindole, poly-1,5-diaminoanthraquinone, polyaminodiphenyl, poly(o-phenylenediamine), poly(quinolinium) salt, polypyridine, polyquinoxaline, polyphenylquinoxaline, and the like. Of these, polypyrrole, polyaniline, and polythiophene are preferred, and polypyrrole is more preferred.
  • the fuel cell electrode catalyst layer preferably further comprises a polymer electrolyte.
  • the polymer electrolytes are not particularly limited as long as being those commonly used in fuel cell catalyst layers. Specific examples thereof include perfluorocarbon polymers having a sulfonic acid group (such as NAFION (registered trademark)), hydrocarbon polymer compounds having a sulfonic acid group, polymer compounds doped with inorganic acids such as phosphoric acid, organic/inorganic hybrid polymers partially substituted with proton conductive functional groups, and proton conductors composed of a polymer matrix impregnated with a phosphoric acid solution or a sulfuric acid solution. Of these, NAFION (registered trademark) is preferable. Examples of the source of NAFION (registered trademark) in forming the fuel cell catalyst layer include a 5% NAFION (registered trademark) solution (DE521, DuPont) and the like.
  • the fuel cell electrode catalyst layer may be used as an anode catalyst layer or a cathode catalyst layer.
  • the fuel cell electrode catalyst layer of the present invention comprises the catalyst that has high oxygen reducing ability and is resistant to corrosion in acidic electrolytes even at high potential and is therefore useful as a catalyst layer provided in a cathode of a fuel cell (as a cathode catalyst layer).
  • the catalyst layer is preferably provided in a cathode of a membrane electrode assembly in a polymer electrolyte fuel cell.
  • the catalyst may be dispersed on the electron conductive particles serving as a carrier by methods such as airborne dispersion methods and in-liquid dispersion methods.
  • the in-liquid dispersion methods are preferable because a dispersion of the catalyst and the electron conductive particles in a solvent can be used in the step for forming a fuel cell catalyst layer.
  • Exemplary in-liquid dispersion methods include a method using orifice-choked flow, a method using rotational shear flow, a method using ultrasonic, and the like.
  • the solvents used in the in-liquid dispersion methods are not particularly limited as long as the catalysts or the electron conductive particles are not corroded and are dispersed therein. Volatile liquid organic solvents, water or the like are generally used.
  • the electrolyte described above and a dispersant may be further dispersed together.
  • the fuel cell catalyst layer may be formed by any methods without limitation.
  • a suspension containing the catalyst, the electron conductive particles, and the electrolyte may be applied to an electrolyte membrane or a gas diffusion layer as described later.
  • the application methods include dipping, screen printing, roll coating, spraying, and the like.
  • a suspension containing the catalyst, the electron conductive particles, and the electrolyte may be applied or filtered on a substrate to form a fuel cell catalyst layer, and the catalyst layer may be transferred to an electrolyte membrane.
  • the electrode produced by the method for producing an electrode of the present invention comprises the fuel cell catalyst layer and a porous support layer.
  • the electrode may be used as any electrode of a cathode or an anode.
  • the electrode of the present invention has excellent durability and high catalytic performance, and therefore using the electrode as a cathode leads to higher industrial advantage.
  • the porous support layer is a layer which diffuses gas (hereinafter also referred to as a "gas diffusion layer").
  • the gas diffusion layer is not limited as long as having electron conductivity, high gas diffusion properties, and high corrosion resistance.
  • Carbon-based porous materials such as carbon paper and carbon cloth, and stainless steel and anticorrosive-coated aluminum foils for weight reduction are generally used as the gas diffusion layer.
  • the membrane electrode assembly produced by the method for producing a membrane electrode assembly of the present invention comprises a cathode, an anode, and an electrolyte membrane interposed between the cathode and the anode, wherein at least one of the cathode and the anode is the electrode produced by the method for producing an electrode of the present invention.
  • electrolyte membranes perfluorosulfonic acid-based electrolyte membranes or hydrocarbon electrolyte membranes are generally used, and there may also be used membranes in which polymer microporous membranes are impregnated with liquid electrolyte; membranes in which porous bodies are filled with polymer electrolyte; or the like.
  • the fuel cell produced by the production method of the present invention comprises the membrane electrode assembly.
  • the electrode reaction in fuel cells takes place at a so-called three-phase interface (electrolyte-electrode catalyst-reactant gas).
  • the fuel cells are classified according to the electrolytes used, into several types such as molten carbonate type (MCFC), phosphoric acid type (PAFC), solid oxide type (SOFC), polymer electrolyte type (PEFC), and the like.
  • MCFC molten carbonate type
  • PAFC phosphoric acid type
  • SOFC solid oxide type
  • PEFC polymer electrolyte type
  • the membrane electrode assembly of the present invention is preferably used in polymer electrolyte fuel cells.
  • the fuel cell using the fuel cell electrode catalyst produced by the production method of the present invention has high performance and is considerably inexpensive as compared with platinum catalysts.
  • the fuel cell has at least one function selected from the group consisting of electricity generating function, light emitting function, heat generating function, sound generating function, movement function, display function, and charging function and can improve the performance of an article, particularly a mobile particle, having a fuel cell.
  • the fuel cell is held preferably on the surface or inside of the article.
  • the fuel cell using the fuel cell electrode catalyst produced by the production method of the present invention has high activity per unit mass and is inexpensive, so that the fuel cell is enabled to be also carried by the above-described articles that have been conventionally difficult to carry a fuel cell and the article with a smaller volume can utilize a high power, thereby preferably leading to functional enhancement.
  • the articles that can comprise the fuel cell include architectural structures such as buildings, houses and tents, illumination equipment such as fluorescent light, LED, organic EL, street light, interior illumination and traffic light, machinery, automotive devices including vehicles, household appliances, agricultural equipment, electronic devices, mobile information terminals including mobile phones, beauty instruments, portable tools, sanitary goods such as bathroom goods and lavatory goods, furniture, toys, ornaments, bulletin boards, cool boxes, outdoor goods such as exterior generators, teaching materials, artificial flowers, items of artwork, power source for cardiac pacemakers and power source for heating and cooling apparatuses equipped with Peltier elements.
  • illumination equipment such as fluorescent light, LED, organic EL, street light, interior illumination and traffic light
  • machinery automotive devices including vehicles, household appliances, agricultural equipment, electronic devices, mobile information terminals including mobile phones, beauty instruments, portable tools, sanitary goods such as bathroom goods and lavatory goods, furniture, toys, ornaments, bulletin boards, cool boxes, outdoor goods such as exterior generators, teaching materials, artificial flowers, items of artwork, power source for cardiac pacemakers and power source for heating and cooling apparatuses
  • the fuel cell using the fuel cell electrode catalyst produced by the production method of the present invention is useful since the fuel cell has high power performance per unit mass and is inexpensive, so that the fuel cell is enabled to be also carried by the articles that have been conventionally difficult to carry a fuel cell and wiring for power feeding can be omitted.
  • the noise (N) was the width of the baseline.
  • Carbon About 0.1 g of a sample was weighed and measured with a carbon/sulfur analyzer (EMIA-110 manufactured by HORIBA, Ltd.) .
  • EMIA-110 manufactured by HORIBA, Ltd.
  • Nitrogen oxygen: About 0.1 g of a sample was weighed, was sealed in Ni-Cup, and was then measured with an oxygen/nitrogen analyzer (TC600 manufactured by LECO).
  • Transition metal element titanium, zirconium, iron
  • titanium(IV) sulfate aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.
  • a mixed liquid of 100 ml of 28% ammonia water and 200 ml of distilled water was prepared, and the above-described titanium solution was dropwise added to the mixed liquid to generate a precipitate (titanium compound).
  • the reaction liquid was allowed to stand for 1 hour, and then supernatant liquid was removed with a dropping pipette so that 100 ml of the reaction liquid (containing the precipitate) remained.
  • the reaction liquid containing the precipitate was centrifuged at 10000 rpm for 30 minutes, followed by removing supernatant liquid with a dropping pipette so that the precipitate and the supernatant liquid remained in an amount of 20 ml in total in a container. Then, a series of operations of adding 80 ml of pure water into the container, stirring the contents in the container, performing the centrifugation in the same manner as described above, and removing supernatant liquid in the same manner as described above was repeated three times to obtain 20 ml of liquid containing a gelatinous substance. Titanium hydroxide is considered to be contained in the gelatinous substance.
  • This powder for heat treatment was put in a tubular furnace, was heated to 1000°C under the atmosphere of a nitrogen gas at a temperature-raising rate of 10°C/min, was held at 1000°C for 3 hours, and was allowed to natural cooling, to obtain a catalyst (1).
  • the mixture was ultrasonically stirred to give a suspended mixture.
  • a glassy carbon electrode (diameter: 5.2 mm, manufactured by Tokai Carbon Co., Ltd.), 30 ⁇ l of this mixture was applied and was dried at 120°C for 5 minutes, thereby forming 1.0 mg of a fuel cell catalyst layer on the carbon electrode surface.
  • the fuel cell electrode prepared was subjected to polarization in a 0.5 mol/L sulfuric acid aqueous solution at 30°C under an oxygen atmosphere and a nitrogen atmosphere at a potential scanning rate of 5 mV/sec to a less potential side, starting from 1.1 V, thereby recording each current-potential curve.
  • the current value was divided by each electrode area, and a value obtained by subtracting the current density observed in the nitrogen atmosphere from the current density observed in the oxygen atmosphere was defined as an oxygen reduction current density.
  • a reference electrode a reversible hydrogen electrode was used in a sulfuric acid aqueous solution of the same concentration.
  • the oxygen reduction current density at 0.7 V is listed in Table 1. The higher the oxygen reduction current density is, the higher the catalytic performance of the catalyst in the fuel cell electrode is.
  • Example 2 The same operation as in Example 1 was carried out, except that 0.85 g of polyvinylpyrrolidone was changed to 2.80 g of N-acetyl-D-glucosamine (Wako Pure Chemical Industries, Ltd., Purity: 90%), to obtain a catalyst (2).
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (2), to obtain a fuel cell electrode (2), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 2 The same operation as in Example 2 was carried out, except that 9.12 g of a 30% titanium sulfate aqueous solution was changed to 3.3 g of a titanium tetrachloride aqueous solution (titanium content: 16.5 mass%, manufactured by OSAKA Titanium Technologies Co., Ltd.), to obtain a catalyst (3).
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (3), to obtain a fuel cell electrode (3), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 2 The same operation as in Example 1 was carried out, except that 0.85 g of polyvinylpyrrolidone was changed to 11.1 g of glycine (manufactured by Wako Pure Chemical Industries, Ltd., purity: 99%), to obtain a powder for heat treatment.
  • This powder for heat treatment was put in a tubular furnace, was heated to 900°C under the atmosphere of a mixed gas of 4% by volume of hydrogen and 96% by volume of nitrogen at a temperature-raising rate of 10 °C/min, was held at 900 °C for 3 hours, and was allowed to natural cooling, to obtain a catalyst (4).
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (4), to obtain a fuel cell electrode (4), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 4 The same operation as in Example 4 was carried out, except that 11.1 g of glycine was changed to 11.1 g of glycine (Wako Pure Chemical Industries, Ltd., purity: 99%) and 0.202 g of iron(II) acetate (manufactured by Aldrich, purity: 95%), to obtain a catalyst (5).
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (5), to obtain a fuel cell electrode (5), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 5 The same operation as in Example 5 was carried out, except that the heat treatment temperature was changed to 500 °C, to obtain a catalyst (6).
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (6), to obtain a fuel cell electrode (6), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 5 The same operation as in Example 5 was carried out, except that the heat treatment temperature was changed to 1200°C, to obtain a catalyst (7).
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (7), to obtain a fuel cell electrode (7), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 2 The same operation as in Example 1 was carried out, except that 0.85 g of polyvinylpyrrolidone was changed to 1.40 g of D (+) -glucose (Wako Pure Chemical Industries, Ltd., purity: 98%), to obtain a catalyst (8).
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (8), to obtain a fuel cell electrode (8), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (9), to obtain a fuel cell electrode (9), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 5 The same operation as in Example 5 was carried out, except that 9.12 g of the 30% titanium(IV) sulfate aqueous solution was changed to 1.51 g of zirconium oxynitrate dihydrate (Wako Pure Chemical Industries, Ltd., purity: 97%), to obtain a catalyst (10) .
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (10), to obtain a fuel cell electrode (10), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 5 The same operation as in Example 5 was carried out, except that 9.12 g of the 30% titanium(IV) sulfate aqueous solution was changed to 1.72 g of niobium (V) pentaethoxide (Wako Pure Chemical Industries, Ltd., purity: 99.9%) and the solvent was changed from water to ethanol, to obtain a catalyst (11).
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (11), to obtain a fuel cell electrode (11), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • titanium oxide product name: SUPER-TITANIA F-6, Showa Denko K.K., anatase type, BET specific surface area: 100 m 2 /g
  • carbon black Vulcan XC72, Cabot Corporation
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (c1), to obtain a fuel cell electrode (c1), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 4 The same operation as in Example 4 was carried out, except that 20 ml of the liquid containing the gelatinous substance was changed to 1.18 g of amorphous titanium oxide (Wako Pure Chemical Industries, Ltd., amorphous, vapor phase synthesis (by the vapor phase method)), to obtain a catalyst (c2).
  • amorphous titanium oxide Wako Pure Chemical Industries, Ltd., amorphous, vapor phase synthesis (by the vapor phase method)
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (c2), to obtain a fuel cell electrode (c2), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • a powdery catalyst (c3) was obtained by heating 0.30 g of the catalyst (c1), obtained in Comparative Example 1, in a mixed gas of 1% by volume of oxygen, 4% by volume of hydrogen, and 95% by volume of nitrogen for 10 hours.
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (c3), to obtain a fuel cell electrode (c3), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • a portion of the resultant material was put in an alumina boat, the temperature of the portion was increased from room temperature (about 25°C) to 800°C at a temperature-raising rate of 150°C/h while circulating nitrogen at a flow rate of 200 ml/min, and the same temperature was maintained for 3 hours to obtain a catalyst (c4) .
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (c4), to obtain a fuel cell electrode (c4), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 5 The same operation as in Example 5 was carried out, except that the heat treatment temperature was changed to 400 °C, to obtain a catalyst (c5).
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (c5), to obtain a fuel cell electrode (c5), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Example 6 The same operation as in Example 6 was carried out, except that the heat treatment temperature was changed to 1300°C, to obtain a catalyst (c6).
  • Example 1 Further, the same operation as in Example 1 was carried out, except that the catalyst (1) was changed to the catalyst (c6), to obtain a fuel cell electrode (c6), and the oxygen reducing ability thereof was evaluated. The result is listed in Table 1.
  • Table 1 Proportion of the Number of Atoms BET Specific Surface Area m 2 /g Oxygen Reduction Current Density mA/cm 2 @ 0.7 V Ti Zr Nb Fe C N O
  • Example 1 Catalyst (1) 1 1.02 0.13 0.88 273 0.16
  • Example 2 Catalyst (2) 1 1.60 0.20 0.61 165 0.31
  • Example 3 Catalyst (3) 1 1.24 0.15 1.05 277 0.32
  • Example 4 Catalyst (4) 1 2.10 0.05 1.46 311 0.73
  • Example 5 Catalyst (5) 0.97 0.03 1.97 0.07 1.13 296 1.03
  • Example 6 Catalyst (6) 0.97 0.03 2.54 0.07 1.52 96 0.15
  • Example 7 Catalyst (7) 0.97 0.03 1.85 0.06 1.24 280 0.33
  • Example 8 Catalyst (8) 1 1.40 0.13 0.43 223 0.25
  • Example 9 Catalyst (9) 1 0.71 0.04 0.89 243 0.12
  • Catalyst (c1) 1 0.52 0.48 0.01 1.8 0.01
  • Catalyst (c2) 1 1.01 0.09 1.70 275 0.02
  • Catalyst (c3) 1 0.10 0.01 1.88 4.2 0.05
  • Catalyst (c4) 1 0.57 0.06 1.87 21 0.033
  • Catalyst (c5) 0.97 0.03 3.66 0.08 1.78 23 0.02
  • Catalyst (c6) 0.97 0.03 1.78 0.05 1.15 266 0.07

Claims (10)

  1. Procédé de fabrication d'un catalyseur d'électrode pour une pile à combustible, comprenant:
    une étape (I) consistant à mettre en contact une solution aqueuse d'un composé de métal de transition (1) avec de l'ammoniaque et/ou de l'eau ammoniacale afin de générer un précipité (A) contenant un atome du métal de transition,
    une étape (II) consistant à mélanger au moins le précipité (A), un composé organique (B) et un milieu liquide (C) pour obtenir un précurseur de catalyseur, et
    une étape (IV) consistant à faire subir au précurseur de catalyseur un traitement thermique à une température de 600 à 1200°C afin d'obtenir un catalyseur d'électrode;
    une partie ou la totalité du composé de métal de transition (1) étant un composé contenant, comme élément de métal de transition, au moins un élément de métal de transition M1 sélectionné parmi les éléments du groupe 4 et du groupe 5 du tableau périodique; et
    le composé organique (B) étant un composé organique contenant de l'azote,
    caractérisé en ce que le procédé comprend en outre une étape (III) consistant à éliminer le milieu liquide (C) du précurseur de catalyseur avant l'étape (IV),
    le rapport (C/A) du nombre total C des atomes d'azote du composé organique contenant de l'azote utilisé à l'étape (II) au nombre total A des atomes des éléments de métal de transition des composés de métal de transition utilisés dans le procédé vaut 1 ou plus et 28 ou moins.
  2. Procédé de fabrication d'un catalyseur d'électrode pour une pile à combustible selon la revendication 1, dans lequel l'élément de métal de transition M1 est au moins un élément sélectionné parmi le titane, le zirconium, le niobium et le tantale.
  3. Procédé de fabrication d'un catalyseur d'électrode pour une pile à combustible selon la revendication 1 ou 2, dans lequel le composé de métal de transition (1) est au moins un sélectionné dans le groupe composé d'halogénures de métal, de sulfates de métal, d'alcoxydes de métal, d'acétates de métal, de phosphates de métal, de nitrates de métal, de sels d'acides organiques de métal, d'halogénures d'acide de métal, de perhalates de métal, d'hypohalites de métal, et de complexes de métal.
  4. Procédé de fabrication d'un catalyseur d'électrode pour une pile à combustible selon l'une quelconque des revendications 1 à 3, comprenant en outre une étape consistant à mélanger un composé contenant, comme élément de métal de transition, au moins un élément de métal de transition M2 sélectionné parmi le fer, le nickel, le chrome, le cobalt et le manganèse, dans l'étape (II).
  5. Procédé de fabrication d'une couche de catalyseur d'électrode pour une pile à combustible, comprenant une étape consistant à fabriquer un catalyseur d'électrode pour une pile à combustible par le procédé selon l'une quelconque des revendications 1 à 4, et une étape consistant à former une couche de catalyseur d'électrode pour une pile à combustible en utilisant un matériau de formation d'une couche de catalyseur comprenant le catalyseur d'électrode pour une pile à combustible.
  6. Procédé de fabrication d'une d'électrode pour une pile à combustible comprenant une couche de catalyseur d'électrode pour une pile à combustible et une couche de support poreuse, le procédé comprenant une étape consistant à fabriquer une couche de catalyseur d'électrode pour une pile à combustible par le procédé selon la revendication 5, et une étape consistant à former la couche de catalyseur d'électrode pour une pile à combustible sur une surface de la couche de support poreuse.
  7. Procédé de fabrication d'un ensemble d'électrode à membrane comprenant une cathode, une anode, et une membrane d'électrolyte placée entre la cathode et l'anode, le procédé comprenant une étape consistant à fabriquer une électrode pour une pile à combustible par le procédé selon la revendication 6, et une étape consistant à placer la cathode, la membrane d'électrolyte et l'anode de façon à fabriquer un ensemble d'électrode à membrane tout en utilisant l'électrode pour une pile à combustible comme au moins une de la cathode et de l'anode.
  8. Procédé de fabrication d'une pile à combustible, comprenant une étape consistant à fabriquer un ensemble d'électrode à membrane par le procédé selon la revendication 7, et une étape consistant à fabriquer une pile à combustible en utilisant l'ensemble d'électrode à membrane.
  9. Procédé de fabrication d'une pile à combustible selon la revendication 8, dans lequel la pile à combustible est une pile à combustible à électrolyte polymère.
  10. Procédé de fabrication d'un catalyseur d'électrode pour une pile à combustible selon la revendication 1, dans lequel le composé contenant de l'azote est au moins un composé sélectionné parmi les sucres aminés, les glycosaminoglycanes, les composés polymères contenant de l'azote, les composés contenant des groupes nitrile et les acides aminés.
EP12748862.5A 2011-02-21 2012-01-04 Procédé de fabrication d'un catalyseur d'électrode pour pile à combustible Active EP2680351B1 (fr)

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PCT/JP2012/050008 WO2012114778A1 (fr) 2011-02-21 2012-01-04 Procédé de fabrication d'un catalyseur d'électrode pour pile à combustible

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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103035914A (zh) * 2013-01-08 2013-04-10 浙江大学 硫化镍薄片/石墨烯复合材料及其制备方法和应用
CN103295756B (zh) * 2013-05-31 2016-05-04 西北师范大学 一种磁性氮掺杂碳材料的制备方法
KR20150088006A (ko) * 2014-01-23 2015-07-31 삼성에스디아이 주식회사 연료전지용 전극 촉매, 그 제조방법, 이를 포함한 연료전지용 전극 및 연료전지
US10547902B2 (en) 2014-07-18 2020-01-28 Sony Corporation Information processing apparatus and method, display control apparatus and method, reproducing apparatus and method, and information processing system
US10005066B2 (en) 2014-11-28 2018-06-26 Showa Denko K.K. Catalyst carrier and method for producing the same
KR101975970B1 (ko) 2016-12-23 2019-05-08 이화여자대학교 산학협력단 중공 복합체, 이의 제조 방법, 및 이를 포함하는 전기촉매
CN109004241B (zh) * 2018-08-09 2021-05-14 南京大学连云港高新技术研究院 一种铁-氮-石墨碳材料的制备方法
KR20210115529A (ko) * 2020-03-13 2021-09-27 현대자동차주식회사 용출된 전이금속이 제거된 연료전지용 촉매 잉크의 제조방법
WO2022066427A1 (fr) * 2020-09-28 2022-03-31 Hyzon Motors Inc., A Corporation In The State Of Delaware Électrodes à tolérance d'inversion de pile améliorée par l'intermédiaire d'oxydes métalliques fonctionnalisés et stabilisés
CN113097502A (zh) * 2021-03-22 2021-07-09 青岛创启新能催化科技有限公司 一种以氮掺杂碳为载体的碳载铂催化剂的制备方法
CN114843476A (zh) * 2022-05-20 2022-08-02 重庆大学 一种v3s4@c/g复合电极材料的制备方法及其应用
CN115925001A (zh) * 2022-12-22 2023-04-07 浙江大学山东工业技术研究院 Ta2O5/NiO复合空心纳米球材料及其制备方法和应用

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7125820B2 (en) 2002-07-31 2006-10-24 Ballard Power Systems Inc. Non-noble metal catalysts for the oxygen reduction reaction
JP2004079244A (ja) * 2002-08-12 2004-03-11 Toshiba Corp 燃料電池用触媒及び燃料電池
JP4463490B2 (ja) 2003-03-31 2010-05-19 独立行政法人科学技術振興機構 遷移金属炭化物からなる電極触媒
JP3969658B2 (ja) 2003-06-27 2007-09-05 純一 尾崎 燃料電池用電極触媒、それを用いた燃料電池および電極
JP2005034779A (ja) * 2003-07-16 2005-02-10 Nissan Motor Co Ltd 電極触媒およびその製造方法
JP5082187B2 (ja) 2003-10-06 2012-11-28 日産自動車株式会社 固体高分子型燃料電池用電極触媒粒子の製造方法
JP5199575B2 (ja) * 2003-10-29 2013-05-15 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト 水電解用の貴金属酸化物触媒
US8062552B2 (en) * 2005-05-19 2011-11-22 Brookhaven Science Associates, Llc Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates
US7605107B2 (en) * 2005-09-29 2009-10-20 Exxonmobil Research And Engineering Company Method of preparing a supported hydrotreating catalyst
JP2007123195A (ja) * 2005-10-31 2007-05-17 Nissan Motor Co Ltd 触媒の製造方法
WO2007072665A1 (fr) 2005-12-19 2007-06-28 National University Corporation Yokohama National University Électrode d’oxydoréduction pour pile à combustible directe
JP4649379B2 (ja) * 2006-07-31 2011-03-09 株式会社東芝 燃料電池用電極、膜電極複合体および燃料電池、ならびにそれらの製造法
JP2008258150A (ja) 2007-03-09 2008-10-23 Sumitomo Chemical Co Ltd 燃料電池用電極触媒
CA2680251A1 (fr) 2007-03-09 2008-09-18 Sumitomo Chemical Company, Limited Ensemble membrane-electrode et pile a combustible utilisant l'ensemble membrane-electrode
JP2008258152A (ja) 2007-03-09 2008-10-23 Sumitomo Chemical Co Ltd 膜−電極接合体およびこれを用いた燃料電池
WO2008111569A1 (fr) 2007-03-09 2008-09-18 National Institute Of Advanced Industrial Science And Technology Catalyseur d'électrode pour pile à combustible
JP2008289971A (ja) 2007-05-23 2008-12-04 Toyota Motor Corp コアシェル構造体及びその製造方法並びに当該コアシェル構造体を含む排ガス浄化用触媒
JP2009023887A (ja) 2007-07-20 2009-02-05 Dainatsukusu:Kk カーボン含有チタンオキシナイトライドと、それを用いた選択吸収膜および太陽光集熱器と、多孔体
US8889315B2 (en) 2007-09-07 2014-11-18 Showa Denko K.K. Catalyst, process for preparing the same, and uses of the catalyst
KR101202104B1 (ko) 2008-02-28 2012-11-15 쇼와 덴코 가부시키가이샤 촉매 및 그 제조 방법 및 그 용도
JP5353287B2 (ja) 2008-03-21 2013-11-27 住友化学株式会社 電極触媒の製造方法および電極触媒
JP2010227843A (ja) * 2009-03-27 2010-10-14 Sumitomo Chemical Co Ltd 電極触媒の製造方法および電極触媒
US7964526B2 (en) * 2009-04-29 2011-06-21 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
WO2011099493A1 (fr) 2010-02-10 2011-08-18 昭和電工株式会社 Procédé de production de catalyseur d'électrode de pile à combustible, procédé de production d'oxycarbonitrure de métal de transition, catalyseur d'électrode de pile à combustible et leurs utilisations
FR2959735B1 (fr) * 2010-05-06 2012-06-22 Rhodia Operations Composition a base d'oxydes de zirconium, de cerium d'au moins une autre terre rare, a porosite specifique, procede de preparation et utilisation en catalyse.
US20120148483A1 (en) * 2010-08-02 2012-06-14 Rongrong Chen Macrocycle modified ag nanoparticulate catalysts with variable oxygen reduction activity in alkaline media
DK2638588T3 (da) * 2010-11-12 2023-03-13 Celcibus Ab Brændselscelleelektrode med porøs carbon-kerne med makrocykliske metal-chelater derpå

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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Publication number Publication date
CN103380523A (zh) 2013-10-30
JPWO2012114778A1 (ja) 2014-07-07
US10026968B2 (en) 2018-07-17
US20130330659A1 (en) 2013-12-12
CN103380523B (zh) 2016-12-07
WO2012114778A1 (fr) 2012-08-30
EP2680351A1 (fr) 2014-01-01
EP2680351A4 (fr) 2016-06-22
JP5153967B2 (ja) 2013-02-27

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